EP2740716A1 - Application of hybrid systems MgO-SiO2 / multiwalled olygomeric silsesquioxanes as promoters of ceramization in silicone composites for covers of electrical cables - Google Patents

Application of hybrid systems MgO-SiO2 / multiwalled olygomeric silsesquioxanes as promoters of ceramization in silicone composites for covers of electrical cables Download PDF

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EP2740716A1
EP2740716A1 EP20130460078 EP13460078A EP2740716A1 EP 2740716 A1 EP2740716 A1 EP 2740716A1 EP 20130460078 EP20130460078 EP 20130460078 EP 13460078 A EP13460078 A EP 13460078A EP 2740716 A1 EP2740716 A1 EP 2740716A1
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ceramization
weight parts
olygomeric
multiwalled
promoters
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French (fr)
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EP2740716B1 (en
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Jan Dul
Grzegorz Parys
Pedzich Zbigniew
Dariusz Bielinski
Teofil Jesionowski
Ambroziewicz Damian
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Instytut Inzynierii Materialow Polimerowych i Barwnikow
Instytut Nawozow Sztucznych
Politechnika Lodzka
Akademia Gomiczo Hutnicza
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Instytut Inzynierii Materialow Polimerowych i Barwnikow
Instytut Nawozow Sztucznych
Politechnika Lodzka
Akademia Gomiczo Hutnicza
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    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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    • C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
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    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3436—Alkaline earth metal silicates, e.g. barium silicate
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
    • C04B2235/3472—Alkali metal alumino-silicates other than clay, e.g. spodumene, alkali feldspars such as albite or orthoclase, micas such as muscovite, zeolites such as natrolite
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    • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
    • C04B2235/483—Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Definitions

  • the subject of invention is application of hybrid systems MgO•SiO 2 / multiwalled olygomeric silsesquioxanes as promoters of ceramization in silicone composites destined for covers of electrical cables.
  • silicone composites containing inorganic particles undergoing ceramization on fire, is commonly known in the cable industry. It is aimed to produce fire resistant electrical cables, which are able to provide electricity supply to electrical circuits and receivers during fire. They can find use in buildings or other objects of higher fire requirements therefore ensure increased safety during fire.
  • Such composites are made of silicone elastomers filled with pyrogenic silica. They are able to thermal vulcanization under the influence of organic peroxides, antypirenes and metallic or mineral compounds being ceramically active at high temperature.
  • Promoters and activators of ceramization process are very important components of ceramizable silicone composites, responsible for initiation and support of ceramic skeleton formation, which preserves cable cover from destruction during fire. With increasing temperature, organic parts of polymer phase degrade and ceramically active components of mineral phase are not able to assure expected mechanical strength of the material only by adhesion forces.
  • the high rate of ceramization of the composite material makes thereby the outer, formed under high temperature, ceramic layer of cable cover, very effective in thermal insulation. It positively affects the sustainability of the physical properties of the cover and formation of ceramic layer of advantageous mechanical properties, what results in prolonged functionality of electrical cables on fire or the action of high temperature.
  • silica as a precursor of ceramization is known from the publication " Ceramic - modified elastomers", published in Current Opinion in Solid State and Materials Science 1999, vol. 4, pp. 565 - 570, by J.E. Mark .
  • use of silica nanoparticles brings about some technical limitations associated with high cost of their production and problems of dispersion in non-polar silicone polymer phase.
  • Hybrid systems composed of silicate base and from 0.1 to 50 weight parts, preferably 10 weight parts, of silsesquioxanes containing R 1 - R 8 , where R 1 to R 8 is alkyl- group and/or groups, or alkoxy-, or methacryloxy-, orglycidoxy-, or amino-, orvinyl-, or perfluoro- or their mixture, are known from the Polish patent declaration P-394903 . They are synthesized by chemical functionalization of the filler surface with alkoxysilanes, followed by mechanical and chemical modification.
  • the essence of the invention is application of the hybrid systems M g O•SiO 2 /multiwalled olygomeric silsesquioxanes, in silicone composites containing magnesium silicate and from 0.1 to 50 weight parts of the silsesquioxanes containing R 1 - R 8 , where R 1 to R 8 is alkyl- group and/or groups, or alkoxy-, or methacryloxy-, or glycidoxy-, or amino-, or vinyl-, or perfluoro- or their mixture, used for its modification, as promoters of ceramization in the silicone composites destined for covers of electrical cables.
  • the amount of platinum catalyst added assured platinum content in the elastomer equal to 50 ppm.
  • Silica filled polymer phase is then cooled down to temperature 110°C, and 45 weight parts of quartz powder, 5 weight parts of wollastonite, 2 weight parts of titanium dioxide and 5 weight parts of the hybrid systems MgO•SiO 2 /multiwalled olygomeric silsesquioxanes, containing 10 weight parts of silsesquioxane octa-substituted with methacrylo- groups on 100 weight parts of magnesium silicate filler, are admixed.
  • silicone composite subjected to curing with 1.5 weight % of bis(2,4-dichlorobenzoyl) peroxide during 15 minutes at 120 °C, exhibits the properties listed below: Results Requirements of cable industry Tensile strength [MPa] 7.7 min. 5.0 Elongation at break [%] 247 min. 150 Tear strength [kN/m] 16 min. 12 Hardness [°Sh A] 64 70 ⁇ 5 Time to ceramization of cured composite under the flame from gas burner at 1050 °C [s] below 60
  • the amount of platinum catalyst added assured platinum content in the elastomer equal to 50 ppm.
  • Silica filled polymer phase is then cooled down to temperature 80°C, and 35 weight parts of potassium mica, 10 weight parts of aluminum hydroxide, 3 weight parts of magnesium hydroxide, 2 weight parts of titanium dioxide and 8 weight parts of the hybrid systems MgO•SiO 2 /multiwalled olygomeric silsesquioxanes, containing 20 weight parts of silsesquioxane octa-substituted with methacrylo- groups on 100 weight parts of magnesium silicate filler, are admixed.

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Abstract

The invention solves the problem of application of the hybrid systems MgO•SiO2/multiwalled olygomeric sisesquioxanes as promoters of ceramization in the silicone composites destined for covers of electrical cables. The systems are composed of magnesium silicate and from 0.1 to 50 weight parts, favourably 10 weight parts, of the silsesquioxanes containing R1 - R8, where R1 to R8 is alkyl-group and/or groups, or alkoxy-, or methacryloxy-, or glycidoxy-, or amino-, or vinyl-, or perfluoro- or their mixture, used for its modification.

Description

  • The subject of invention is application of hybrid systems MgO•SiO2 / multiwalled olygomeric silsesquioxanes as promoters of ceramization in silicone composites destined for covers of electrical cables.
  • Application of silicone composites containing inorganic particles, undergoing ceramization on fire, is commonly known in the cable industry. It is aimed to produce fire resistant electrical cables, which are able to provide electricity supply to electrical circuits and receivers during fire. They can find use in buildings or other objects of higher fire requirements therefore ensure increased safety during fire.
  • Such composites are made of silicone elastomers filled with pyrogenic silica. They are able to thermal vulcanization under the influence of organic peroxides, antypirenes and metallic or mineral compounds being ceramically active at high temperature.
  • Promoters and activators of ceramization process are very important components of ceramizable silicone composites, responsible for initiation and support of ceramic skeleton formation, which preserves cable cover from destruction during fire. With increasing temperature, organic parts of polymer phase degrade and ceramically active components of mineral phase are not able to assure expected mechanical strength of the material only by adhesion forces.
  • Activity of promoters and precursors plays also an important role in the rate of ceramic layer formation of the cable cover. According to actual state-of-the art it should meet expected mechanical properties at the temperature of 900 - 1100°C and no later than after 60 s.
  • The high rate of ceramization of the composite material makes thereby the outer, formed under high temperature, ceramic layer of cable cover, very effective in thermal insulation. It positively affects the sustainability of the physical properties of the cover and formation of ceramic layer of advantageous mechanical properties, what results in prolonged functionality of electrical cables on fire or the action of high temperature.
  • Application of fme particles silica as a precursor of ceramization is known from the publication "Ceramic - modified elastomers", published in Current Opinion in Solid State and Materials Science 1999, vol. 4, pp. 565 - 570, by J.E. Mark. However, use of silica nanoparticles brings about some technical limitations associated with high cost of their production and problems of dispersion in non-polar silicone polymer phase.
  • Able to oxidation compounds of magnesium, chemically reacting at high temperature with silica and/or aluminum compounds and producing such minerals as forsterite (Mg2SiO4), magnesium silicate (MgSiO3), cordierite (2Mg•2Al2O3-5SiO2), spinel (MgAl2O4), which are the components of the ceramic outer layer formed, are known from the patent declaration US 2009/0099289 . Important drawback of the above solution concerns the fact, that magnesium oxide, produced in high temperature oxidation of magnesium compounds, should quantitatively react up with silica and/or other components of mineral phase. Otherwise, the unreacted magnesium oxide left can adversely affect electrical insulation properties of cable cover.
  • The above problem does not occur if, products of hydrolysis of phenyltrichlorosilane (C6H5SiCl3) and methyltrichlorosilane (CH3SiCl3), synthesized by known methods - described in the patent declaration P-397997, are used as precursor of ceramization.
  • In the patent declaration P-397998, another precursor of ceramization, namely tetraethoxysilane adsorbed on the surface of diatomite powder, has been presented. At the temperature of 120±10°C, under the influence of water contained in diatomite powder, rapid hydrolytic destruction of tetraethoxysilane occurs, resulting in highly reactive nanosilica particles formation on the surface of diatomite particles. Simultaneously an excess of moisture and ethanol, produced in the hydrolysis reaction, is evaporating.
  • Hybrid systems composed of silicate base and from 0.1 to 50 weight parts, preferably 10 weight parts, of silsesquioxanes containing R1 - R8, where R1 to R8 is alkyl- group and/or groups, or alkoxy-, or methacryloxy-, orglycidoxy-, or amino-, orvinyl-, or perfluoro- or their mixture, are known from the Polish patent declaration P-394903 . They are synthesized by chemical functionalization of the filler surface with alkoxysilanes, followed by mechanical and chemical modification.
  • The essence of the invention is application of the hybrid systems MgO•SiO2/multiwalled olygomeric silsesquioxanes, in silicone composites containing magnesium silicate and from 0.1 to 50 weight parts of the silsesquioxanes containing R1 - R8, where R1 to R8 is alkyl- group and/or groups, or alkoxy-, or methacryloxy-, or glycidoxy-, or amino-, or vinyl-, or perfluoro- or their mixture, used for its modification, as promoters of ceramization in the silicone composites destined for covers of electrical cables.
  • Application of the above mentioned hybrid systems makes possible to obtain a composite mix of high susceptibility to ceramization, which is able to produce well developed ceramic layer, effectively protecting metal wire of electrical cable from heat transfer and possible melting during fire.
    • Example no. 1
  • 40 weight parts of pyrogenic silica, having the specific surface area of 200 m2/g and platinum catalyst in the form of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane are admixed to 100 weight parts of dimethyl-vinyl siliconeof average molecular weight Mw= 680 000 and vinyl group content of 0.07 %, at 140°C. The amount of platinum catalyst added assured platinum content in the elastomer equal to 50 ppm. Silica filled polymer phase is then cooled down to temperature 110°C, and 45 weight parts of quartz powder, 5 weight parts of wollastonite, 2 weight parts of titanium dioxide and 5 weight parts of the hybrid systems MgO•SiO2/multiwalled olygomeric silsesquioxanes, containing 10 weight parts of silsesquioxane octa-substituted with methacrylo- groups on 100 weight parts of magnesium silicate filler, are admixed.
  • Prepared in this way silicone composite, subjected to curing with 1.5 weight % of bis(2,4-dichlorobenzoyl) peroxide during 15 minutes at 120 °C, exhibits the properties listed below:
    Results Requirements of cable industry
    Tensile strength [MPa] 7.7 min. 5.0
    Elongation at break [%] 247 min. 150
    Tear strength [kN/m] 16 min. 12
    Hardness [°Sh A] 64 70±5
    Time to ceramization of cured composite under the flame from gas burner at 1050 °C [s] below 60
    • Example no. 2
  • 40 weight parts of pyrogenic silica, having the specific surface area of 200 m2/g and platinum catalyst in the form of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane are admixed to 100 weight parts of dimethyl-vinyl silicone of average molecular weight Mw = 680 000 and vinyl group content of 0.12 %, at 140°C. The amount of platinum catalyst added assured platinum content in the elastomer equal to 50 ppm. Silica filled polymer phase is then cooled down to temperature 80°C, and 35 weight parts of potassium mica, 10 weight parts of aluminum hydroxide, 3 weight parts of magnesium hydroxide, 2 weight parts of titanium dioxide and 8 weight parts of the hybrid systems MgO•SiO2/multiwalled olygomeric silsesquioxanes, containing 20 weight parts of silsesquioxane octa-substituted with methacrylo- groups on 100 weight parts of magnesium silicate filler, are admixed.
  • Prepared in this way silicone composite, subjected to curing with 1.5 weight % of bis(2,4-dichlorobenzoyl)peroxide during 15 minutes at 120 °C, exhibits the properties listed below:
    Results Requirements of cable industry
    Tensile strength [MPa] 6.1 min. 5.0
    Elongation at break [%] 207 min. 150
    Tear strength [kN/m] 18 min. 12
    Hardness [°Sh A] 73 70±5
    Time to ceramization of cured composite under the flame from gas burner at 1050 °C [s] below 60

Claims (1)

  1. Application of the hybrid systems MgO•SiO2/multiwalled olygomeric sisesquioxanes, in silicone composites containing magnesium silicate and from 0.1 to 50 weight parts of the silsesquioxanes, favourably 10 weight parts, containing R1 - R8, where R1 to R8 is alkyl- group and/or groups, or alkoxy-, or methacryloxy-, orglycidoxy-, or amino-, or vinyl-, or perfluoro- or their mixture, used for its modification, as promoters of ceramization in the silicone composites destined for covers of electrical cables.
EP20130460078 2012-11-29 2013-11-26 Application of hybrid systems MgO-SiO2 / multiwalled olygomeric silsesquioxanes as promoters of ceramization in silicone composites for covers of electrical cables Not-in-force EP2740716B1 (en)

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PL401810A PL219849B1 (en) 2012-11-29 2012-11-29 The use of hybrid MgO.SiO <sub> 2 /polyhedral oligomeric silsesquioxanes as promoters of ceramization in silicon composites for covering electrical wires</sub>

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EP2740716A1 true EP2740716A1 (en) 2014-06-11
EP2740716B1 EP2740716B1 (en) 2015-01-21

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CN114989617B (en) * 2022-06-06 2023-05-02 浙江葆润应用材料有限公司 Preparation method of ceramic silicone rubber material with strong weather resistance

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